CN104925798A - Triangular graphene preparing method - Google Patents
Triangular graphene preparing method Download PDFInfo
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- CN104925798A CN104925798A CN201510363363.6A CN201510363363A CN104925798A CN 104925798 A CN104925798 A CN 104925798A CN 201510363363 A CN201510363363 A CN 201510363363A CN 104925798 A CN104925798 A CN 104925798A
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Abstract
A triangular graphene preparing method includes 1, washing the surface of a metal copper sheet, placing into a tubular furnace, evacuating till the certain vacuum degree, and heating until the temperature ranges from 900 to 1100 DEG C in the hydrogen atmosphere; 2, maintaining the calcination temperature for 0.5 to 1.5 hour, feeding a carbon source gas into the tubular furnace, allowing the volume ratio of the carbon source gas and the hydrogen to range from 5 : 4 to 5 : 6, and maintaining the total pressure to be 5 Torr; allowing graphene to grow for 1 to 50min, and depositing the graphene on the calcined metal material; 3, switching off the carbon source gas, feeding inert gas, allowing the volume ratio of the hydrogen and inert gas to range from 1 : 8 to 1 : 12, cooling the graphene until the temperature ranges from 800 to 900 DEG C, switching off the hydrogen, and cooling the graphene till room temperature in the inert gas. The preparing method is simple and is adaptive to large-scale production; the produced graphene material has the advantages of novel appearance and controllability, structure is stable, the metal copper sheet can be removed completely, and the graphene material is prevented from contamination.
Description
Technical field
The invention belongs to field of functional materials.
Background technology
Graphene, as a kind of novel two-dimension nano materials, is the Two Dimensional Free state atomic crystal of the unique existence found at present.Since self-discovery, Graphene not only receives very big concern in pure science, and due to its special nanostructure and excellence physical and chemical performance and show at numerous areas such as Materials science, catalysis, solid state physics, electronics, biomedicine, magnetics, optics, nano electrochemical, sensor and energy storage there is huge application potential.Current people have utilized the reduction of mechanically peel, silicon carbide carbon epitaxial method, graphite oxide, chemical vapor deposition (CVD) legal system for Graphene.Wherein chemical vapour deposition (CVD) method preparation method is simple, and gained Graphene quality is higher, is a kind of method of the most potential large-scale industry growing graphene at present.But the Graphene pattern of preparation is difficult to control, and comparatively common are irregular Graphene, hexagon, tetragon, dodecagon are also reported to some extent.Trilateral Graphene rarely has report, accurately control the pattern of Graphene for the distinctive physical property of exploration Graphene, and the application expanded in lithium ion battery, fuel cell, ultracapacitor and various energy storage field is significant.
Summary of the invention
The present invention seeks to a kind of preparation method of trilateral Graphene.
The preparation method of the trilateral Graphene described in the present invention, comprises the following steps.
(1) by metal copper sheet surface cleaning, put into tube furnace, and be drawn into certain vacuum degree, in hydrogen atmosphere, be heated to temperature 900-1100 DEG C.
(2) maintain institute calcining temperature 0.5-1.5h, in described tube furnace, pass into carbon-source gas, making it with the volume ratio of hydrogen is 5:4-5:6, and maintenance total pressure is 5Torr.Carry out the growth of Graphene, growth 1-50min, deposited graphite alkene on metallic substance after firing.
(3) close carbon-source gas, passing into rare gas element, is be cooled to 800-900 DEG C in 1:8-1:12 in the volume ratio of hydrogen and rare gas element, closes hydrogen, in rare gas element, is cooled to room temperature.
Metal copper sheet surface cleaning described in step (1), the metal copper sheet that the method removing Graphene of conventional dissolved copper covers can be adopted, available nitric acid (massfraction is the salpeter solution of 20%-35%) dissolves, or removes with iron nitrate (concentration is 1.0-2.0 g/ml) and ammonium persulphate (concentration is 3.0-8.0 g/ml).Preferred: by metallic substance successively with Glacial acetic acid, nitric acid, cleaning drying up with nitrogen.
Step (2) described carbon source is the organic molecule gas of carbon containing, as methane, acetylene, and optimization methane.The preferred 40-60sccm of airshed.
Rare gas element described in step (3) is argon gas or nitrogen, preferred argon gas.The preferred 30-50sccm of gas flow.
Trilateral Graphene prepared by the present invention is two-dirnentional structure, and described trilateral is right-angle triangle, and trilateral is not of uniform size, shape is similar, is close and numerously distributed in whole substrate, and Graphene both can be individual layer or bilayer, also can be three layers or more than, or list, polyhybrid layer.
The metal of load trilateral Graphene provided by the present invention and Graphene both as electrode materials, can be used for energy storage as energy storage material again.
Trilateral Graphene provided by the present invention is a kind of novel graphite alkene pattern.In crystalline-granular texture, it is different from traditional regular hexagon, tetragon, dodecagon structure, neither equilateral triangle structure, but the triangular structure of right angle of novelty.This special structure, most important for the physical property disclosing Graphene special, thus lay the foundation in the industrial applications of the energy for it.
The present invention has following useful effect: (1) the present invention makes public for the first time the triangular structure of right angle of Graphene.Preparation technology is simple, can be mass-produced.(2) the trilateral Graphene prepared by the present invention has novel in shape, controllable advantage.(3) the present invention's metal copper sheet used can remove completely, can not pollute grapheme material.(4) the present invention the grapheme material Stability Analysis of Structures arrived sent out, convenient transport.(5) the trilateral Graphene that the present invention obtains can directly be used for carrying out physical property detection, and applies in energy related products.
Accompanying drawing explanation
Fig. 1 is the experimental installation structural representation that trilateral Graphene is prepared in invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of trilateral Graphene prepared by the present invention.
Fig. 3 is the opticmicroscope figure of trilateral Graphene prepared by embodiment 1.
Fig. 4 is the Raman spectrogram of multilayer trilateral Graphene prepared by embodiment 1.
Fig. 5 is the Raman spectrogram of the individual layer of embodiment 2 preparation and the trilateral grapheme material of two-layer hybrid.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail:
Method described in embodiment below, if no special instructions, is ordinary method; Described material agents, if no special instructions, all can obtain from commercial channels.
Embodiment 1.
The first step, cleaning copper sheet.
Copper sheet is used successively Glacial acetic acid, deionized water, salpeter solution 10s(concentrated nitric acid: deionized water=1:3), deionized water, Glacial acetic acid, deionized water respectively clean 3min, dry up with nitrogen afterwards.
Second step, calcining copper sheet.
Copper sheet as shown in Figure 1, is put into tube furnace silica tube, is evacuated down to 70Pa by experimental installation used, passes into hydrogen 40sccm, is heated to 1040 DEG C.
3rd step, growing graphene.
Holding temperature 1040 DEG C of 0.5h, pass into methane 50 sccm, maintenance total pressure is 5Torr, growth 5min, closes carbon source, opens Ar40sccm, hydrogen furnishing 4sccm, close hydrogen after being cooled to 900 DEG C, cool to room temperature in Ar atmosphere, namely obtain the trilateral Graphene that the number of plies is individual layer and two-layer hybrid.
4th step, removing metal copper sheet.
Preparation PMMA solution (solute is polymethacrylate, and solvent is chlorobenzene, 46mg/ml), by the metal copper sheet spin coating PMMA of load Graphene, 130 DEG C of baking 5min, so that PMMA solidification.Put into ammonium persulphate 2-5h, until copper sheet dissolves completely; By washed with de-ionized water at least 3 times, finally in deionization, place 30min; Bottom graphene film, Graphene is held up, 220 DEG C of baking 5min with the silicon chip of acetone ultrasonic cleaning.Put into acetone 2h, Virahol 30min respectively, deionized water 10min cleans PMMA and residual solution, 300 DEG C of baking 5min, obtain trilateral Graphene.
5th step, the sign of material.
The Graphene that 4th step obtains is carried out scanning electron microscope sign (Fig. 2), and graphene-structured is right-angle triangle as figure shows, and the triangular right-angle length of side is about 1 μm, is evenly distributed.
Embodiment 2.
After the present embodiment is warmed up to assigned temperature, constant temperature time is different, preparation method by embodiment 1: after copper sheet surface cleaning, put into tube furnace, be evacuated down to 70Pa, pass into hydrogen 40sccm, be heated to 1040 DEG C, holding temperature 1h, pass into methane 50 sccm, maintenance total pressure is 5Torr, growth 5min, closes carbon source, opens Ar40sccm, hydrogen furnishing 4sccm, close hydrogen after being cooled to 900 DEG C, cool to room temperature in Ar atmosphere, namely obtain the trilateral Graphene of individual layer and two-layer hybrid.
Embodiment 3.
Different temperature is cooled to, the preparation method by embodiment 1: after copper sheet surface cleaning, put into tube furnace during the present embodiment cooling, be evacuated down to 70Pa, pass into hydrogen 40sccm, be heated to 1040 DEG C, holding temperature 0.5h, passes into methane 50 sccm, and maintenance total pressure is 5Torr, growth 5min, closes carbon source, opens Ar40sccm, hydrogen furnishing 4sccm, close hydrogen after being cooled to 800 DEG C, cool to room temperature in Ar atmosphere, namely obtain the trilateral Graphene of multilayer.
Embodiment 4.
Different hydrogen is passed into, the preparation method by embodiment 1: after copper sheet surface cleaning, put into tube furnace during the present embodiment cooling, be evacuated down to 70Pa, pass into hydrogen 40sccm, be heated to 1040 DEG C, holding temperature 0.5h, passes into methane 50 sccm, and maintenance total pressure is 5Torr, growth 5min, closes carbon source, opens Ar40sccm, hydrogen furnishing 5sccm, close hydrogen after being cooled to 900 DEG C, cool to room temperature in Ar atmosphere, namely obtain the trilateral Graphene of multilayer.
Claims (6)
1. a preparation method for trilateral Graphene, is characterized in that comprising the following steps:
(1) by metal copper sheet surface cleaning, put into tube furnace, and be drawn into certain vacuum degree, in hydrogen atmosphere, be heated to temperature 900-1100 DEG C;
(2) maintain institute calcining temperature 0.5-1.5h, in described tube furnace, pass into carbon-source gas, making it with the volume ratio of hydrogen is 5:4-5:6, and maintenance total pressure is 5Torr; Carry out the growth of Graphene, growth 1-50min, deposited graphite alkene on metallic substance after firing;
(3) close carbon-source gas, passing into rare gas element, is be cooled to 800-900 DEG C in 1:8-1:12 in the volume ratio of hydrogen and rare gas element, closes hydrogen, in rare gas element, is cooled to room temperature.
2. the preparation method of trilateral Graphene according to claim 1, is characterized in that step (2) described carbon source is the organic molecule gas of carbon containing.
3. the preparation method of trilateral Graphene according to claim 1 and 2, is characterized in that step (2) described carbon source is methane or acetylene.
4. the preparation method of trilateral Graphene according to claim 1, is characterized in that the airshed of step (2) described carbon-source gas is 40-60sccm.
5. the preparation method of trilateral Graphene according to claim 1, is characterized in that the rare gas element described in step (3) is argon gas or nitrogen.
6. the preparation method of trilateral Graphene according to claim 1, is characterized in that the rare gas element gas flow described in step (3) is 30-50sccm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105906750A (en) * | 2016-04-18 | 2016-08-31 | 青岛大学 | Method for controlling intelligent deformation of CVD graphene |
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